Catalyst preparation



. CATALYST PREPARATION James B. Hunter, Upper Darby, lagualgnor to The Atlantic Refining Company, Philadelphia, Pa., a corporation ot Pennsylvanla No Drawing. Application April 17, 1946, Serial No. 662,934

4 Claims. 1 e The presentinvention relates to the preparation of silica-alumina catalysts of improved stability, and relates more particularly to the pro-y duction of silica-alumina catalysts containing acid adsorptive alumina, which catalysts are suitsteam stability. It is therefore an object of this invention to prepare unimproved silica-alumina catalyst, the alumina constituent of which is characterized by itshigh acid adsorptivity and steam stability, thereby imparting to the catalyst as a whole, such desirable property. In addition able for use in the conversion or refining of hy- 5 to improved stability, the catalysts produced in drocarbons, especially petroleum and fractions accordance with this invention are further charthereof. aeterized by their unusual hardness and resista In the production of gasoline and other fuels, ancetobreakdown during use. it has been conventional practice to crack higher In accordance with this invention, there is proboiling hydrocarbon oils in the presence of varivided a novel method for combining silica with ous catalysts, including silica-alumina composialumina, wherein silica gel is caused to form tions in the form of finely divided particles or in through the agency of, and in intimate contact the form of granules or pellets. These catalysts, with, the alumina. The alumina here employed after use, become fouled with carbonaceous mais one of high acid adsorptivity, the preparation a d e a y e enerated fi st y s ripof which will be described hereinafter in detail. ping out entrained oil by contacting with steam. In carrying out this invention, an alkali metal 'ggdthglcfigminghofii the carbongcious deltiosllts silicate solution such as an aqueous solution of 2w 8 W1 a r a r an 5 m a fisodium silicate is treated with an exces oi minmtefl l' mperatures. However, it has e n found eral acid, such as dilute hydrochloric o: sulfuric that the cracking activity ofthe catalysts deteacid, whereby there 1 obtained a clear solution riorates upon repeated use and regeneration, and having a pH not in excess or 3, and preierably h t the commercial silica-alumina catalysts between 1 and 2. At this relatively low pH, no b f y Sensitive to Steaming and have precipitation or gelation of silica occurs and the a relatively poorsteam stability. These catalysts product comprises a 5111 which is aistinctly I ifitttlifiitistfifiifit ot tffifieiielfifi pifif rag fifl f is added eipitated hydrated silica gel is suspended in a i ln t to :irovi e $1: desire: 5111 13? solution of an aluminum, salt, and the alumina is the final sinca alumma catalyst e mixture is precipitated in the silica gel by the addition of th h] it ted to if 1 h an alkali hydroxide or ammonia. In a second m? 2': 5m i i method, purified silica and alumina hydrogels mediate! comlenence 0 :urfac if g which have been separately prepared are intig b m e n mately mixed, dried, and activated by heating. i fi 7 a1 9 Pb0 0f3 e mix lilre gradlliaa y In a third method,'silica hydrogel is saturated r W and pre era a We with a solution of an aluminum sa1t,and the 2: w on Po the m sets to mm mixture is heated to decompose the salt and dee be m the the posit alumina on the silica. The catalysts pre t hquor for penods up to about 15 days H pared by these and other prior art methods rapsued and than thoroughly washed to efiect reidly lose their conversion eiiiciency, due in part 40 g g if be to the present methods of regeneration. Since 8 lmme The steaminghas been found to be the most efiective mg be f i water i an way of removing entrained oil from the spent mg s mmuon' or mm a dilute mmeral catalyst prior to thermal regeneration in the F solution followed by water" The washed presence of air, it is apparent that any improve- .then dried remove free water grinulai-ed by ment in the heat stability, and particularly the Bumble means and by j at steam stability, of the catalyst will constitute a Dentures between Z and 9 and pref marked advantage erably between 900 F. and 1000 F. prepar- It has been observed that the alumina constit mg the silica-alumina catalyst, the ratio of silica uent of the prior art silica-alumina catalysts has to alumina may be varied as j In genera-1' a very low capacity for the adsorption of hydroof 5mm to alumina withfn the range or gen ions, e. g., mineral acids, such as dilute hy- 19:1 1:3 has e mund atlsfacton" those drochloricacid, and may generally be charactercatalysts in which the alumna predommates ized as non-acid adsorptive alumina. It'has also usually being the most stable' been observed that the steam stability of the In Producing the alumina a hlgh acid prior art silica-alumina catalysts is relatively low. adsorptivity and a high heat stabmty' an aquelusr on the other hand, it has been found that a solution of aluminum sulfate is reacted with an tam of prepared under certain con aqueous Solution Of 811 metal bicarbonate, dltions has a high acid adsorptivity and a good or a mixture of carbonate and bicarbonate, of which the latter constitutes at least 50%. While it v is possil'llir to use chemically equivalent amounts of-aluminum sulfate and bicarbonate or carbonate-bicarbonate mixture. or to use an excess of aluminum sulfate over bicarbonate or carbonate-bicarbonate, it has beembeen found that the best results are obtained using an excess of bicarbonate orcarbonate-bicarbonate over aluminum sulfate. It is preferred to employ a total equivalent ratio of bicarbonate or carbonate-bi carbonate of about 1.3, or in other words about 30% eiicess alkali over that theoretically required for complete reaction with the aluminum sulfate. This ratio may vary somewhat, but should be maintained within the range of 1.1 to 1.5 to obtain aluminas of highest acid adsorptivityand heat stability. Best results have been obtained using alkali bicarbonate, per se, although suitable aluminasmaybe prepared using carbonate-bicarbonate mixtures in which the bicarbonate represents at least 50% of the mixture. When the amount of bicarbonate is less than about 50%, the stability of the alumina decreases markedly, the lowest stability being attained using carbonate, per se. The use of'soluble aluminum salts such as the chloride and nitrate, with alkali metal bicarbonate or carbonate-bicarbonate mixtures gives aliuninas of mediocre acid adsorptivity and very poor heat stability, as well as of gelatinous structure and poor fllterability. Similarly, the production of aluminas by the treatmentof any soluble aluminum salt, including the sulfate, with strong alkalis such as sodium, potassium. or ammonium hydroxidesyields poor quality products having negligible acid adsorptivities and poor stability. a jj Incarrying out the preparation of the improve aluminas, it is preferred to use reactant solutions of relatively high concentration, since high cencentration appears to beneficially affect the resulting alumina. To this end, it is desirable to use solutions having. a normality of at least. 1,

a"i'idgspre fe'rably between 2 and 4. The reaction between thealuminum sulfate andlthe alkali metal bicarbonate orcarbonate-bicarbonate may be carried outat ordinary temperatures (60 F. to 80 F.) or at somewhat higher or lower temperatures without adverse effect. In the preferred method of operation, the aluminumsulfate solution is made up, and to this is added the bicarbonate solution in the required amount. When both'bicarbonate and carbonate are used, the necessary amount of bicarbonate solution is added first, and the carbonate solution is thereafter added. :However, the order of addition may be reversed, or a mixture of bicarbonate and carbonate may he made up in a single solution, and

' such solutionadded to the aluminum sulfate solu-.

tion. During the addition of the alkali to the sulfate solution, vigorous agitation is maintained, and upon completion of the addition, the reactant solution containing the aluminamay be immediately filtered to remove the alumina, .or the alumina may be aged in the reaction liquor 'for a suitable period prior to the filtration or other treatment. It has been found, in general, that ageing of the alumina in the reaction liquor for periods up to about days, gives products of substantially higher acid adsorptivity and heat stability than aluminas which are immediately removed from the reaction liquor and washed.

However, regardless. of whether or not the alumina is aged, such alumina may ultimately be Washed with water or aqueous solutions containing ammonium salts in order to remove residual alkali metal compounds.

' In order to illustrate thepreparation of aluminas of high acid a'dsorptivity and stability suit able for use in accordance with the present invention, as compared with other aluminas not suitable, the following examples are given.

Various amounts of 1 N NaHCOa, 1 N NasCOa, and 1 N NaOH alone and in various ratios to'each other were added dropwise, at F. andwith vigorous agitation, to 650 cc. portions of"2 N aluminum salt solutions. This quantity of aluminum salt yielded approximately 22 grams of alumina (dry basis). After precipitation, the alumina slurry was divided into two equal parts. One part was washed immediately with 3 separate portions of 500 cc. each of distilled water, with 5 minutes stirring per wash. After each wash the alumina was filtered on a Buchnerifunnel under vacuum (15 inches mercury). Following the last wash andfiltration, the cake was repulped with 250 cc. of distilled water, stirred for 5 minutes, and stored in a pint bottle. The second portion of the original slurry (containing the reaction liquor) was stored in a one quart bottle for a period of one week. The slurry was then filtered and washed according to the precedure given above. The washed alumina was then repulped in 250 cc. of distilled water, and stored in a. pint bottle. The concentration of alumina in the testsamples was therefore 11 grams per 2502cc. of

water. The samples thus prepared were then subjected to tests for acid adsorptivity and heat stability. 7

The slurry sample was vigorously agitated in the bottle and then poured into a 2 inch Buchner funnel under vacuum (15 inches of mercury);

The water was thus removed from the alumina which formed a small, compact cake which eventually cracked. After the cake has cracked, the vacuum was released, and two samples of the alumina were taken from the cake by means of a small, open-ended glass cylinder having a length of 3 cm,, inside diameter 1.5 cm., and outside diameter 1.75 cm. The quantity of alumina exactly filling thisyvolun'ie was designated as 1 gel unit. One gei unit was placed in each of two 400cc. beakers and cc. of distilled water was added toproduce. a thin slurry. The pH of the slurry was determined electrometrlcally, during agitation, and acid adsorptivity was measured by adding approximately 0.1 N hydrochloric acid (0.0953 N HCl) in 10 cc. increments, allowing a suitable period of time to attain an equilibrium pH, which time'never exceeded 5 minutes. Increments of hydrochloric acid were added until the pH of the slurry fell we value below 3. The

date may then be plotted as pH against cc. of 0.1 N HCl. and the number of cc. of 0.1"N HCl.

required to lower the pH of the, slurry from 4.5

transferred to, a tray of water (60 F.-80 F.)," 'where the slurry was continuously, stirred until the temperaturehad dropped below F. After reaching room temperature (70 F.), the sample was titrated with hydrochloric acid as described above. The stability was deflned'as the number of co. oi 0.1 N Hill required to lower the pH of the heat treated slurry from a value of 4.5 to 3.5.

Na2O.3.43SiO2) was diluted 5 6 The results obtained in the various system vigorous agitation, to the acid-stabilized silica are given in the following table: sol as above prepared. when the alumina was all... awa-rurco -morr V a l Alumina,Washed Aluminmlged-Washed N agl rl xl b s't'diiibfilfitt I 10.6mm Stability Adsorption Stability 1.000 1.000 106 4 194 12 asss 1.000 m s as a 0.000 1.000 40 a s a 8 mm AiOh-NaHOOr-NqOO;

mnoogncl. NaHOOrI-N COJAIOh 1.000 1.000 110 2a 130 11 0.838 1.:00 00 s 110. 11 0.500 I. 78 3 00 8 0.000 1.000 100 a s4 14 System IIAHOQPNGHOOPNQGCM NaHC so Nine 1 9 nacwflk ooi 1.s00 1.100 am 27s 017 200 uses 1.000 1 a: 2st no as 0:600 1.300 216 60 310 141 0.000 1.300 324 107 299 110 From the above data, it will be seen that in order to produce aluminas having a high acid adsorptivity and stability. it is necessary to employ aluminum sulfate and an alkali-metal bicarbonate, or a carbonate-bicarbonate combination in which the bicarbonate predominates. In each of the above examples,the entire quantity of bicarbonate was added first. and the remaining alkali required, 1. e., carbonate or hydroxide was then added. It will be observed that in most cases, ageing of the alumina in the reaction liquor for 7 days. prior to washing, resulted in a marked increase in adsorptivity and stability. In preparing the silica-alumina catalysts oi the present invention, it is preferred to use aluminas having an acid adsorptivity of at least 300 and a stability 01' at least 200. in order to obtain the desired properties in the ultimate catalyst com- Position.

I The production of the silica-alumina catalyst according to the present invention is illustrated by'the-following example, which, however, is not 50 to be construed as limiting theacope thereof. The quantities of reactants were calculated to give a catalyst comprising 85% silica and alumina.

443cc. of commercial sodium silicate solu- 65 tion (an aqueous solution containing 36% with 1290- cc. of water, and to this solution was added 141 cc. of concentrated hydrochloric acid (36.7% H01) diluted with 710 cc. of water. The resulting acidstabilized silica sol was a clear solution having a DH of 2.

An acid adsorptive alumina was prepared by reacting an aqueous aluminum sulfate solution (2N) with an aqueous solution of sodium bicarbonate (INL, the ratio oi sulfate to bicarbonate being 1 to 1.3. The resulting alumina was separated from the reactant solution, and was thoroughly washed with water to remove sodium sulfate and excess bicarbonate. The alumina, when 7 tested as set forth herelnbeiore, had an acid ad sorptivity of 302 and a stability oi 273. This alumina was made up into a slurry with water (37 grams ofAlzO: onadrybasis,madeupto813 grams of slurry), and the slurry was added, with 40 acid, and then dried at uniformly dispersed in the sol, aci'd adsorption immediately set in, and within about 1 minute the pH oi the mixture rose to 4.8. Alter permitting the mixture to stand, a white, glassy, opaque, fairly stir! mixed gel set in about 8 minutes. The silica-alumina gel was then broken up and allowed to stand quiescent for 18 hours, after which it was washed 8 times with 2.5 liters of water containing 2.5 cc. of concentrated hydrochloric acid. The gel was then washed 4 times with 2.5 liters of water to remove the hydrochloric 220 F. to remove free water. The resulting dried gel was exceedingly hard, and upon wetting with a small amount of water, broke down into small granules of the order 01' 20 to 30 mesh size, which granules were hard and glasslike. The-granules were redried at 220 F., ground and screened to 40-325 mesh,

and activated by heating for 1 hour at 932 F. in

the presence of air. For use in the so-called "fluid catalytic cracking operations, only ilne mesh catalyst is suitable. whereas in the "fixed bed" cracking processes, the catalyst is usually formed into pellets approximately 4 mesh.

It has been observed that in those processes in which the used catalyst is contacted with steam to remove entrained oil prior to regeneration with air at elevated temperatures of the order of 900 F. to 1100 F., the rate oi. diminution oi catalytic activity is most rapid during the early period of use, and generally levels out over an extended period of use. This rapid diminution at the outset appears to be duedorshe most part to the eflectof the stripping steam, the eflects or the thermal regeneration with air beingoi minor importance. Therefore, in order to determine the stability of the catalyst, an accelerated test has been devised which simulates the conditions encountered during the early period of catalyst use where the decline of catalytic activity is most pronounced. In this test the catalyst is contacted 0 with steam at 1050 F. for 30 hours, and the cracking activity is then determined. and compared with the cracking activity 01 fresh. unsteamed catalyst. The results thus obtained are indicative oi. the stability of the catalyst. In carrying out the cracking activity test, 25 cc. of the powdered catalyst is placed in a tube and maintained at a temperature of 932 F. and 400 cc. of oil is vaporized and passed through the catalyst in a period of 2 hours. The cracked products are separated, and the quantity of distillate boiling up to 400 1".,

as well as gas and loss is determined, andisdesignated as the distillate plus loss (D+L) It has been found that the catalysts produced in accordance with the present invention and including acid adsorptive alumina show. in genera], a decrease in activity by the steam test of only about whereas the prior art catalysts containing non-acid adsorptive alumina exhibit a. decrease in activity of the order of 25%.

The catalysts of the present invention are useful not only in cracking hi h boiling hydrocarbon oil to produce gasoline, but also in reforming straight-run or cracked gasoline, in polymerizing hydrocarbon gases,'in isomerizing hydrocarbon oils and gases, in desulfurizing and refining oils, and the like. 7

I claim:

1. The method of preparing a silica-alumina catalyst, which comprises mixing with an acidstabilized silica sol having a pH between 1 and 3. an acid adsorptive alumina having an acid adsorptive value of at least 300 and a stability of at least 200 in an amount sumcient to raise the pH of the mixture about 3 by adsorption oi acid from the acid-stabilized sol, said acid adsorptive alumina having been prepared by reacting aluminum sulfate with an alkali metal bicarbonate, permitting the silica-alumina gel formation to occur by the increased pH of the silica sol, and washingacid and soluble salts from the gel.

2. The method of preparing a silica-alumina catalyst, which comprises mixing with an acidstabilized silica sol having a pH between 1 and :3, an acid adsorptive alumina having an acid adsorptive value of at least 300 and a stability of at least 200 in an amount suflicient to raise the pH of the mixture above 3 by adsorption of acid from the acid-stabilized sol, said acid adsorptive alumina having been prepared by reacting aluminum sulfate with an alkali metal bicarbonate, permitting the silica-alumina gel formation to occur by the increased pH of the silica sol. washing acid and soluble salts from the gelt. drying t e gel, and activating the dried gel by heating at elevated temperature.

3. The method of preparing a silica-alumina catalyst, which comprises mixing with an acidstabilized silica sol having a pH between 1 and 3, an acid adsorptive alumina having an acid adsorptive value of at least 300 and a stability of at least 200 in an amount suiiicient to raise the pH of the mixture above 3 by adsorption of acid from the acid-stabilized sol, said acid adsorptive alumina having been prepared by reacting aluminum sulfate with an alkali metal carbonate and bicarbonate of which the bicarbonate constitutes at least 50%. permitting the silica-alumina gel formation to occur by the increased pH of the silica sol, and washing acid and soluble salts from t e gel.

4. The method of preparing a silica-alumin catalyst, which comprises mixing with an acidstabilized silica sol having a PH between 1 and 3. an acid adsorptive alumina having an acid adsorptive value of at least 300 and a stability of at least 200 in an amount suiiicient to raise the 7 DH of the mixture above 3 by adsorption of acid from the acid-stabilized sol, said acid adsorptive. alumina having been prepared by reacting aluminum sulfate with an alkali metal carbonate and bicarbonate of which the bicarbonate constitutes at least 50%, permitting the silica-alumina gel formation to occur bythe increased pH of the silica. sol, washing acid and soluble salts from the gel, drying the gel, and activating the dried gel by heating at elevated tem erature.

JAMES B. HUNTER.

summons crran The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,942,799 Brewer et al. Jan. 9, 1934 2,307,878 Connolly Jan. 12, 1943 2,356,303 Connolly Aug. 22, 1944 2,384,945 Marisic Sept. 18, 1945 1 2,390,272 Riesmeyer et al. Dec. 4, 1945 FOREIGN PATENTS Number Country Date 392,954 GreatBritain May 22, 1933 

